Treatment for improving curl retention,luster,manageability,strength and other mechanical prperties

ABSTRACT

This invention relates to compositions and methods for improving the curl retention, luster, manageability and mechanical properties of human hair. More particularly, it has been unexpectedly found that hair dressing compositions containing a monomeric N-(oxoalkyl) acrylamide or its derivatives contained in a cosmetic carrier can be applied to the hair and the monomeric material polymerized safely thereon to provide the aesthetic and physical properties mentioned above.

United States Patent 1 91 Kinney et a1.

TREATMENT FOR IMPROVING CURL RETENTION, LUSTER, MANAGEABILITY, STRENGTH AND OTHER MECHANICAL PROPERTIES Inventors: James F. Kinney, Ramsey, N.J.;

Anthoni Edward Gadzala, Suffern, NY.

Assignee: Avon Products Inc., Suffern, NY.

Filed: Aug. 8, 1972 Appl. No.: 278,769

US. Cl 132/7, 424/71, 424/DIG. 2 Int. Cl A45d 7/00 Field of Search 132/7; 8/127.51, 128 R, 8/127.6, 128 A, 128 R; 424/72, 70, 71, DIG.

References Cited UNITED STATES PATENTS 1/1972 Anzumo 132/7 1 June 28, 1974 3,634,022 1/1972 Robbins 132/7 3,665,935 5/1972 Kingsh0tt.. 3,676,550 7/1972 Anzumo -132/7 3,678,157 7/1972 Kalopissis ct a1. 132/7 Primary Examiner-G. E. McNeill Attorney, Agent, or FirmPennie & Edmonds [57] ABSTRA(ifT This invention relates to compositions and methods for improving the curl retention, luster, manageability and mechanical properties of human hair. More particularly, it has been unexpectedly found that hair dressing compositions containing a monomeric N- (oxoalkyl) acrylamide or its derivatives contained in a cosmetic carrier can be applied to the hair and the monomeric material polymerized safely thereon to provide the aesthetic and physical properties mentioned above.

8 Claims, N0 Drawings BACKGROUND OF THE INVENTION Hair dressing compositions of various types have been used to alter the appearance and physical properties of human hair. Several compositions have been proposed and are commercially available which are directed to increasing either one or several of the properties of luster, curl retention, manageability, etc., which are commonly desired in the beautification of human hair. Present dyeing, bleaching and hair waving procedures subject the hair to severe chemical changes which often make the hair fibers weaker in mechanical properties, such as tensile strenth.

Among the hair dressing compositions known are those which contain polymeric materials which are deposited on the surface of the hair fibers and increase the physical strength thereof through their additive coating effect. The polymeric materials which are most generally used in these preparations are polymers or copolymers of acrylic acid or methacrylic acid which contain free or neutralized carboxyl groups. These products give only temporary benefit as they are soluble in water and, therefore, are easily removed from the hair through the action of rain, bathing or home showering.

Additionally, preparations have been made which contain adducts of ethylene oXide with other materials such as fatty alcohols. These materials have the ability of increasing the luster and silky appearance to the hair which is most desirable, but do not substantially increase the mechanical properties and curlretentivity of the hair. In the desire to improve the setting and lustering properties of the hair as well as the mechanical properties, compositions containing copolymers of N- substituted acrylamides and acrylic acids or their derivatives have also been used, but these are also not entirely suitable for the reasons set forth above with respect to the other polymeric materials.

In general, the polymeric materials discussed above as well as other ethylenically unsaturated materials which have been used in hair dressing compositions are polymerized prior to application to the hair due to the stringent conditions which are normally required in the polymerization of such materials and the hazards associated in handling the monomeric materials. These stringent conditions, such as elevated temperatures,

inert atmospheres and the like, are not suitable for effecting polymerization on the head of the user. Furthermore, the-coating of these polymeric materials on the hair fibers forms a material which is not cohesively bonded to the hair and, therefore, easily flake off forming an unsightly appearance, or is readily dissolvable therefrom.

SUMMARY OF THE INVENTION It has now been found that certain acrylamide monomer materials can be safely applied to the hair of the user and polymerized in situ to form inside and on the hair shaft a product which renders the hair aesthetically in such a manner as to make it less susceptible to flaking and increases the hairs mechanical properties over coated hair fibers.

The monomeric acrylamides which have unexpectedly been found to produce the desired results are the N-(oxoalkyl) acrylamides and derivatives thereof which can be readily polymerized after application to the hair by various mild and dermotologically acceptable initiating conditions. The N-(oxoalkyl) acrylamide monomers may be polymerized alone or copolymerized with other comonomeric N-substituted acrylamides which are applied to the hair in cosmetic vehicles.

DETAILED DESCRIPTION OF THE INVENTION The acrylamides of the present invention have the general formula:

wherein R, R,,R R and R may be hydrogen, a C, C alkyl such as methyl, ethyl, n-propyl, and the like, a hydroxy C, C alkyl such as hydroxymethyl, hydroxyethyl and the like, or a substituted C, C alkyl wherein the substituted group is an aldehyde, ketone, sulfonate, or a carboxylic acid radical, and Y represents oxygen or an amino C, C alkyl residue.

These acrylamide monomeric materials are easily applied to the hair either alone or in conjunction with additional comonomeric materials which may be represented by:

wherein R is selected from the group consisting of hydrogen, cyano, or a C, C alkyl radical and wherein R and R are selected from the group consisting of hydrogen, C, C alkyl, C, C substituted alkyl of which substitution is selected from hydroxy, alkoxy, carboxyl and oxo groups.

The N-(oxoalkyllacrylamide monomers which are the subject of this invention, may be readily formed from any one of several processes known to those skilled in the art. As an illustration, where R R are hydrogen the monomeric material is produced by the reaction of two moles of acetone with one mole of acrylonitrile in the presence of sulfuric acid to form the product hereinafter called diacetone acrylamide. When the Y substituent of the above general formula is a substituted amino residue, it may be formed by reacting the N-(oxylakyl).acrylamide with a primary amine in a customary manner to form a Schiff base. Diacetone acrylamide is the simplest form of the monomeric material contemplated by this invention. Various derivatives of this compound, where R R and Y are substituted with those groups indicated above, may also be used.

Diacetone acrylamide may, in accordance with the I above general formula, have such alkyl or substituted alkyl groups to replace one or more of the hydrogens which are alpha to the oxo or alkylimino group. The number and specificity of the groups will depend upon the particular application which is desired by the cosmetologist. The increase in number of any one of these groups or a combination of these groups with a hydrophilic containing group will increase the hydrophilic properties of the monomeric material and the resultant polymer.

The reaction of a primary amine with the N- (oxoalkyl) acrylamide yields a Schiff base material. The resultant monomeric product containing the Schiff base moiety alone or in combination with R R substituted groups described above will have increased affinity towards the hair and thus make the monomeric material more accessible to the intersticies of the hair fiber.

The comonomers described above which have been found acceptable are exemplified by acrylamide, methacrylamide, ethacrylamide, dimethyl acrylamide, dimethyl methacrylamide, methylethylacrylamide, diethylmethacrylamide, dimethylolacrylamide, dimethylomethacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, ethoxyethylacrylamide, methoxymethylmethacrylamide, carboxymethyl acrylamide, carboxyethyl acrylamide, N,N-dicarboxyethylacrylamide, betamethylpropionate acrylamide and the like. Salts such as the sodium or potassium salt, of comonomers containing lower alkyl carboxylic acid radical may also be used. In addition, other polymerizable acrylamide comonomers which are well known to those skilled in the art may be used in combination with the N-(oxoalkyl) acrylamide as described hereinabove.

Small amounts of the monomeric material or combinations of monomeric and comonomeric materials may be applied to human hair and polymerized thereon to obtain the desired end results. It has been found that concentrations of N-(oxoalkyl) acrylamide in a cosmetic carrier base may range from about one parts to 25 parts of monomeric material per hundred parts of composition yields satisfactory results. The preferred range of concentration being one parts to parts of monomeric material per hundred parts of composition. Wherein a combination of monomers are used the total concentration of the combined monomers can be from one part to parts of combined monomers per hundred parts of composition. When the concentration of the dicaetone acrylamide or its substituted derivatives is low in such combinations, the concentration of the combined monomers should be closer to the upper end of the range found suitable such as between about five parts to about 10 parts per hundred parts of composition. The concentration of the monomeric materials may range from about one parts to 10 parts of diacetone acrylamide or its substituted derivatives with from about one parts to 10 parts of comonomeric materials based on a total concentration of 100 parts of monomeric and comonomeric material to be used to form a total combined monomeric component.

The monomeric materials are combined with a suitable cosmetic carrier base. These carrier bases are well known to those skilled in the art and include aqueous alcoholic solutions, alcoholic solutions, oil-in-water emulsions, and water-in-oil emulsions. The cosmetic carrier base substantially forms the remaining part of the hair dressing composition of this invention. These new hair dressing compositions containing monomeric diacetone acrylamide or its derivatives as well as combinations of monomeric materials are obtained by simply mixing the monomeric material with the cosmetic carrier vehicle. In some instances, wherein the monomeric material is not completely soluble in the cosmetic carrier, additional solvent for the monomers may be combined with the cosmetic carrier and, if necessary, an emulsifying agent maybe added to cause a homogenous mixture to be formed and thereby allow even distribution of the monomeric material on the hair.

If desired, additional compounds which are conventionally used in hair preparations may be incorporated in the hair dressing composition of this invention. The addition of these compounds will depend upon the specific use and application desired and such additional compounds may include colorants, perfumes, fillers, dyestuffs, thickening agents, and the like.

Hair dressing compositions containing the monomeric materials, as described hereinabove, may be applied to the hair in any known hair dressing manner such as by spraying the composition onto the hair from a spray bottle or by an aerosol container. Alternatively, the composition may be applied to the hair by hand until the hair is saturated with the composition. Such application can be safely done as the monomeric materials disclosed herein are non-toxic.

After application of the hair dressing composition in sufficient amounts to saturate the hair, the monomeric materials can be readily polymerized in a variety of methods. These methods include self-initiation of the polymerization reaction and redox radical initiation mechanisms.

Self initiation of the monomeric materials which have been previously applied to the hair may be induced by the application of heat. The degree of heat need not be such as would cause harm or pain to the user. Suitable amounts of heat to initiate the polymerization are readily obtained through the use of hair dryers, hot combs, hot curlers and the like. In as much as the polymerization is exothermic in nature, the reaction will be selfinitiated once a small degree of heat is applied. The resultant polymerized material will add body to normally or damaged hair by causing the polymerization to occur both in and on the hair fibers.

' Another method for polymerization of the applied monomeric materials is the more familiar redox radical initiation mechanism. The hair dressing compositions may contain small quantities, such as from 0.01 part to 5.00 part, of one of the bicomponents of such redox systems. After application of the hair dressing composition, the hair may then be exposed'to a solution containing the additional component of such redox systems to thus form free radicals which will readily initiate polymerization of the monomeric materials disclosed hereinabove. Alternately, such redox radical initiation may be performed by first applying the hair dressing compositions containing the monomeric material and subsequently applying a freshly prepared solution containing from 0.01 part to 0.10 part of each of the bicomponent redox radical forming materials. Examples of such redox systems include potassium persulfate and sodium bisulfite, potassium persulfate and tetrakis(hydroxyalkyl)phosphonium chloride; ferrous ammonium sulfate and hydrogen peroxide; thioruea and hydrogen peroxide; sodium bisulfite and oxygen; ferrous acetate and organic disulfide compounds; ferrous acetate and organic carboxycylic acids; as well as other well known redox radical initiation systems. Various compounds, such as sodium bisulfite, can auto oxidize by air oxidation to form initiating radicals.

trative purposes only and are not meant to be limiting I upon the inventive concept except as set forth in the appended claims. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE I The vinyl monomeric material diacetone acrylamide was prepared in the conventional manner by reacting acetone with acrylonitrile in the presence of sulfuric acid. Five parts of the product thus formed is mixed with 65 parts of water and 30 parts of ethanol. The composition thus formed is applied to samples of human hair by spraying. After the hair has been thoroughly saturated with the solution, the hair is dried using a conventional hair dryer. During the process of drying the heat thus formed initiated the polymerization of the monomeric material. The treated samples were compared with untreated samples and show marked improvement in luster and manageability and,

when tested, treated samples showed increased tensile strength-over untreated samples;

Skin patch tests were done with the monomeric containing hair dressing composition. Initial observation as well as those conducted after 24 and 48 hours showed no skin irritation.

EXAMPLE n Five parts of diacetone acrylamide is mixed with various vehicle base materials as indicated in Table 1 below.

TABLE I H O/Ethanol Aqueous Shampoo Ethanol v H O-oil emulsion The compositions are applied to the hair by spray application until the hair is thoroughly saturated. The samples are treated with a source of moderate heat to allow self initiation. Each of the samples, when compared with untreated hair, shows marked improvement in tensile strength, luster and curl retentivity.

EXAMPLE III Five parts of omega-hydroxymethyl dicaetone acrylamide are mixed with 95 parts of the carrier base materials indicated-in Table I of Example II above. Human hair samples are treated with the compositions in a manner similar to that described in Example II. Each of the samples, when compared with untreated hair, shows marked improvement in strength, luster and curl retentivity.

EXAMPLE IV The following samples shown in Table II are prepared by mixing the diacetone acrylamide derivative monomers with the indicated substitution with a carrier base material to make a 100 part mixture.

The resultant compositions are applied to the hair in conventional manners until the hair is thoroughly satu rated with the solutions. The method of initiating polymerization and the test results are shown for each sample.

EXAMPLE V Five parts diacetone acrylamide and 5 parts acrylamide are mixed with 30 parts ethanol with 60 parts water to form a composition which is sprayed onto the hair. Polymerization is initiated by the application of heat to the hair. The resultant sample, when compared with an untreated sample, shows marked improvement in luster, curl retention and tensile strength.

EXAMPLE VI EXAMPLE VII Five parts of diacetone acrylamide are mixed with 10 parts of Freon 1 l3 propellant (hp. 1 17F), 10 parts of ethanol and .5 parts of sodium bisulfite. The mixture is poured into an aerosol container and pressurized with 74.5 parts Freon 12. The formulation is applied to hair which has previously been hydrated (through shampooing, rinsing, etc.). After drying the treated hair shows significant improvements in mechanicalproper- EXAMPLE VIII partment. The aerosol is pressurized in the normal manner. On extrusion, the formulation is applied to samples of hair in conventional manners. The treated samples show marked improvements in curl retention and other aesthetic characteristics associated with well groomed hair.

It will be understood that it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purpose of illustration which do not constitute departures from the spirit and scope of the invention.

We claim:

1. A method of improving, the curl retention and strength of human hair which comprises applying a cosmetic carrier base containing monomeric N-substituted acrylamide having the formula:

% III (I111: Ill 1'1 JIIa I l IIU wherein R, R R, R and R are selected from the group consisting of hydrogen, alkyl and substituted groups; said substituted group being a carboxyl, carbonyl, sulfonyl and hydroxy groups and subsequently initiating polymerization of the monomeric material in situ on the hair.

2. A method of improving the curl retention and strength of human hair which comprises applying a cosmetic carrier base containing monomeric N-substituted acrylamide having the formula:

0 H OH; R\ o R3 CH=CH(3I I( J-C l( 3-R m E's 1'1 wherein R R R R and R are selected from the group consisting of hydrogen, alkyl and substituted alkyl groups, said substituted group being a carboxyl,

carbonyl, sulfonyl and hydroxy groups with a comonomeric material having the formula:

wherein R is selected from the group consisting of hydrogen, alkyl and substituted alkyl groups; said substituted group being alkaryl and substituted aryl groups, and subsequently initiating polymerization of the monomeric materials in situ on the hair.

3. A method of claim 1 wherein polymerization is initiated by application of heat.

4. A method of claim 2 wherein polymerization is initiated by application of heat.

5. A method of claim 1 wherein polymerization is initiated by application of a redox catalytic initiation system.

6. A method of claim 2 wherein polymerization is initiated by application of a redox catalytic initiation system.

7. A method of claim 1 wherein polymerization is radical initiated by auto oxidation.

8. A method of claim 2 wherein polymerization is radical initiated by auto oxidation. l l 

2. A method of improving the curl retention and strength of human hair which comprises applying a cosmetic carrier base containing monomeric N-substituted acrylamide having the formula:
 3. A method of claim 1 wherein polymerization is initiated by application of heat.
 4. A method of claim 2 wherein polymerization is initiated by application of heat.
 5. A method of claim 1 wherein polymerization is initiated by application of a redox catalytic initiation system.
 6. A method of claim 2 wherein polymerization is initiated by application of a redox catalytic initiation system.
 7. A method of claim 1 wherein polymerization is radical initiated by auto oxidation.
 8. A method of claim 2 wherein polymerization is radical initiated by auto oxidation. 